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United States Patent |
5,104,559
|
Pawloski
,   et al.
|
April 14, 1992
|
Hydrogen perfluoroalkylaromatic ethers and related compositions and
methods
Abstract
A lubricating compound having the structure:
R.sup.1 --R.sub.f --O--Ar--R.sup.2
wherein R.sup.1 is a monovalent radical selected from the group consisting
of fluoride, unsubstituted aryloxys, substituted aryloxys, unsubstituted
arylthios, substituted arylthios, perfluoroalkoxys, and perfluoro
(3,6-dimethyl-1, 4-dioxanyl-2-oxy), R.sup.2 is a monovalent radical
selected from the group consisting of hydrogen, halides, cyano, nitro,
unsubstituted alkyls having from 1 to 10 carbon atoms inclusive,
perfluoroalkyls having from 1 to 10 carbon atoms inclusive,
perfluoroalkoxys having from 1 to 10 carbon atoms inclusive, substituted
and unsubstituted hydrogen perfluoroalkoxy aryloxys, substituted and
unsubstituted hydrogen perfluoroalkoxy arylthios, unsubstituted alkoxys
having from 1 to 8 carbon atoms inclusive, unsubstituted aryls,
substituted aryls, unsubstituted aryloxys, substituted aryloxy,
unsubstituted alkylthios, substituted arylthios, unsubstituted arylthios,
substituted and unsubstituted arylketones, substituted and unsubstituted
arylsulfones, and substituted and unsubstituted alkylcarboxys, R.sub.f is
a hydrogen perfluoroalkyl divalent radical having from 2 to 10 carbon
atoms inclusive, and AR is an aryl radical. A method for making such
compounds and lubricant compositions containing such compounds are also
disclosed.
Inventors:
|
Pawloski; Chester E. (Bay City, MI);
Inbasekaran; Muthiah N. (Midland, MI)
|
Assignee:
|
The Dow Chemical Company (Midland, MI)
|
Appl. No.:
|
617748 |
Filed:
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November 26, 1990 |
Current U.S. Class: |
508/244; 508/307; 508/434; 508/447; 508/517; 508/545; 508/549; 508/568; 508/569; 508/578; 508/581; 546/301; 549/443; 568/33; 568/49; 568/52; 568/53; 568/54; 568/332; 568/586; 568/588; 568/635; 568/645; 568/647 |
Intern'l Class: |
C10M /; C07C 041/00 |
Field of Search: |
252/48.4,54
568/637,33,49,52,53,54,332,586,588,635,647,645
|
References Cited
U.S. Patent Documents
3265741 | Aug., 1966 | Sheppard | 252/54.
|
4024192 | May., 1977 | Benninger et al. | 252/54.
|
4484008 | Nov., 1984 | Cook, Jr. et al. | 568/33.
|
4792635 | Dec., 1988 | Marhold et al. | 568/332.
|
Foreign Patent Documents |
0084743 | Aug., 1983 | EP | 568/33.
|
3836175 | May., 1990 | DE | 568/54.
|
Primary Examiner: Willis, Jr.; Prince
Assistant Examiner: McAvoy; Ellen
Claims
We claim:
1. A compound having the structure:
R.sup.1 --R.sub.f --O--Ar--R.sup.2
wherein
R.sup.1 is a monovalent radical selected from the group consisting of
aryloxys, arylthios, and perfluoro (3,6-dimethyl-1,4-dioxanyl-2oxy),
R.sup.2 is a monovalent radical selected from the group consisting of
hydrogen, halides, cyano, nitro, alkyls having from 1 to 10 carbon atoms
inclusive, perfluoroalkyls having from 1 to 10 carbon atoms inclusive,
perfluoroalkoxys having from 1 to 10 carbon atoms inclusive, hydrogen
perfluoroalkoxy aryloxys, hydrogen perfluoroalkoxy arylthios, alkoxys
having from 1 to 8 carbon atoms inclusive, aryls, aryloxys, alkylthios,
arylthios, arylketones, arylsulfones, and alkylcarboxys,
R.sub.f is a hydrogen perfluoroalkyl divalent radical having from 2 to 10
carbon atoms inclusive, and
Ar is an aryl radical.
2. The compound of claim 1, wherein
R.sup.1 is selected from the group consisting of --OPhr.sup.2.sub.z ;
--OXOR.sub.f OPhR.sup.2.sub.z ; --SPhR.sup.2.sub.z ; --ONpR.sup.2.sub.z ;
and --OPyR.sup.2.sub.z ;
X is a divalent radical selected from the group consisting of --Ph-- and
--PhQPh--,
Q is a divalent radical selected from the group consisting of --CH.sub.2
--, --C(CF.sub.3).sub.2 --, --C(CH.sub.3).sub.2 --, --SO.sub.2 --, --CO--,
--S--, --O--, --PhC(CF.sub.3).sub.2 Ph--; and --PhC(CH.sub.3).sub.2 Ph--;
Ph is the phenyl radical,
Np is the naphthyl radical,
Py is the pyridyl radical,
m is from 1 to 20 inclusive, and
z is from 1 to 2 inclusive.
3. The compound of claim 1,
wherein R.sup.2 is a monovalent radical selected from the group consisting
of --(OPh).sub.n ; --OPhR.sup.4.sub.z ; --OR.sub.f OPhR.sup.4.sub.z ;
--OR.sub.f SPhR.sup.4.sub.z ; --OR.sub.f ONpR.sup.4.sub.z ; --OR.sub.f
OPyR.sup.4 z; and --C(O)PhR.sup.5.sub.z ;
R.sup.4 is a monovalent radical selected from the group consisting of
hydrogen, halides, cyano, nitro, alkylthios, alkyls, perfluoroalkyls, and
perfluoroalkoxys,
R.sup.5 is a monovalent radical selected from the group consisting of
fluoride, aryloxys, arylthios,
Ph is the phenyl radical,
Np is the naphthyl radical,
Py is the pyridyl radical,
n is from 1 to 4 inclusive, and
z is from 1 to 2 inclusive.
4. The compound of claim 1, wherein R.sup.2 is --C(O)PhF.
5. The compound of claim 1, wherein R.sub.f has from 2 to 6 carbon atoms
inclusive.
6. The compound of claim 1, wherein R.sub.f is a hydrogen perfluoropropyl
divalent group.
7. The compound of claim 1, wherein the compound is stable up to a
temperature of at least 300.degree. C.
8. The compound of claim 1, wherein the compound is selected from the group
consisting of
(a) a benzophenone having the structure:
R.sup.6 PhC(O)PhOR.sub.f R.sup.6 ;
(b) a sulfide having the structure:
R.sup.6 PhOR.sub.f OPhSPhOR.sub.f OPhR.sup.6 ;
(c) a benzosulfone having the structure:
R.sup.6 PhOR.sub.f OPhSO.sub.2 PhOR.sub.f OPhR.sup.6 ;
(d) a benzene-containing compound having the structure:
R.sup.6 PhOR.sub.f OPhOR.sub.f OPhR.sup.6 ;
(e) a bisphenol derivative having the structure:
PhOR.sub.f OPhAPhOR.sub.f OPh; and
(f) an ether having the structure:
R.sup.6 PhOR.sub.f OPhOPhOR.sub.f OPhR.sup.6,
wherein
R.sup.6 is a monovalent radical selected from the group consisting of
hydrogen, halides, alkoxys, aryloxys, and arylthios,
R.sub.f is a hydrogen perfluoroalkyl divalent radical having from 2 to 10
carbon atoms inclusive,
A is a divalent radical selected from the group consisting of
--C(CF.sub.3).sub.2 -- and --C(CH.sub.3).sub.2 --, and
Ph is the phenyl radical.
9. The compound of claim 1, wherein the compound is selected from the group
consisting of:
(a) a benzophenone selected from the group consisting of
4-fluoro-4'-(1-(3-methoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)benzophenone
4-fluoro-4'-(1-(3-phenoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)benzophenone
;
4-phenylthio-4'-(1-(3-phenoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)benzophe
none;
4-fluoro-4'-(1-phenylthio-1,2,3,3,3-pentafluoropropoxy)benzophenone;
4-(3-trifluoromethylphenoxy)-4'-(1-(3-phenoxyphenoxy)-1,2,3,3,3-pentafluoro
propoxy)benzophenone; and
4-(3-phenoxyphenoxy)-4'-(1-phenoxy-1,2,3,3,3-pentafluoropropoxy)benzophenon
e;
(b) a sulfide selected from the group consisting of
bis (4-(3-methoxyphenoxy-1,2,3,3,3,-pentafluoropropoxy)phenyl) sulfide; and
bis (4-(1phenoxy-1,2,3,3,3-pentafluoropropoxy)phenyl)sulfide;
(c) a benzosulfone including
bis(4-(1-phenoxy-1,2,3,3,3-pentafluoroporpoxy)phenyl) benzosulfone;
(d) a benzene-containing compound selected from the group consisting of
1. 3-bis(1-(3-phenoxypehnoxy)-1,2,3,3,3-pentafluoropropoxy)benzene; and
1,3-bis(1-phenoxy-1,2,3,3,3-pentafluoropropoxy) benzene;
(e) a bisphenol derivative selected from the group consisting of
2,2-bis(4-(1-phenoxy-1,2,3,3,3-pentafluoropropoxy)phenyl) propane; and
2,2-bis(4-(1-phenoxy-1,2,3,3,3-pentafluoropropoxy)phenyl)-1,1,1,3,3,3-hexaf
luoropropane; and
(f) an ether selected from the group consisting of
bis(4-(1-(4-(1,1-dimethylethylphenoxy)-1,2,3,3,3-pentafluoropropoxy)phenyl)
ether; and
bis(4-(1-(3-phenoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)phenyl) ether.
10. A lubricant composition comprising from at least about 0.1 to about 100
weight percent of the compound of claim 1.
11. A lubricant composition comprising from about 0.5 to about 50 weight
percent of the compound of claim 1.
12. A lubricant composition comprising from about 5 to about 20 weight
percent of the compound of claim 1.
13. A lubricant composition comprising at least about 50 weight percent of
the compound of claim 1.
14. A lubricant composition comprising at least about 95 weight percent of
the compound of claim 1.
Description
TECHNICAL FIELD
This invention relates generally to hydrogenperfluoroalkyl aromatic ethers
which are useful as lubricant base stocks or lubricant additives and
compositions and methods related to these ethers.
BACKGROUND OF THE INVENTION
The demands placed on lubricants are currently undergoing significant
changes. Engines are being developed for automotive and aeronautic
applications that have requirements dramatically different from those of
engines currently in use. It is anticipated that these engines will
operate at temperatures exceeding 250.degree. C. and will be constructed
using materials new or different from those currently in use. Thus, what
is needed are novel compounds useful as lubricant base stocks or lubricant
additives that are stable at the high use temperatures while possessing
the other properties required of lubricants.
Being stable at high use temperatures means that the desired lubricating
compounds would (1) have low reactivity at elevated temperatures, e.g., be
less oxidative, less hydrolyzable, less reactive to bases, and less
polymerizable, (2) experience little or no decomposition at elevated
temperatures, and (3) have relatively low volatility and high boiling
points.
It is desirable that the new lubricating compounds be highly soluble in
organic oils and greases if they are to be used as lubricant additives. It
would also be beneficial if the new lubricating compounds could be
prepared by simple methods and in high yields.
It is, therefore, a primary object of this invention to provide new
compounds and a method for making such compounds which (1) are useful as
lubricant base stocks or lubricant additives, (2) are stable at high
temperatures, (3) are highly soluble in organic oils and/or greases, and
(4) which can be prepared by relatively simple methods and in high yields.
It is another object of this invention to provide lubricant compositions
containing such compounds.
SUMMARY OF THE INVENTION
In accordance with a preferred embodiment of the invention, these and other
objects and advantages are addressed as follows. A compound having the
structure:
R.sup.1 --R.sub.f --O--Ar--R.sup.2
is disclosed wherein:
R.sup.1 is a monovalent radical selected from the group consisting of
fluoride, unsubstituted aryloxys, substituted aryloxys, unsubstituted
arylthios, substituted arylthios, perfluoroalkoxys, and perfluoro (3,
6-dimethyl-1, 4-dioxanyl-2-oxy),
R.sup.2 is a monovalent radical selected from the group consisting of
hydrogen, halides, cyano, nitro, unsubstituted alkyls having from 1 to 10
carbon atoms inclusive, perfluoroalkyls having from 1 to 10 carbon atoms
inclusive, perfluoroalkoxys having from 1 to 10 carbon atoms inclusive,
substituted and unsubstituted hydrogen perfluoroalkoxy aryloxys,
substituted and unsubstituted hydrogen perfluoroalkoxy arylthios,
unsubstituted alkoxys having from 1 to 8 carbon atoms inclusive,
unsubstituted aryls, substituted aryls, unsubstituted aryloxys,
substituted aryloxys, unsubstituted alkylthios, substituted arylthios,
unsubstituted arylthios, substituted and unsubstituted arylketones,
substituted and unsubstituted arylsulfones, and substituted and
unsubstituted alkylcarboxys,
R.sub.f is a hydrogen perfluoroalkyl divalent radical having from 2 to 10
carbon atoms inclusive, and
Ar is an aryl radical.
Lubricant compositions containing the above-described compounds also form
part of the invention.
The invention also includes a method for forming a lubricating compound,
comprising reacting
(a) a compound having the structure:
R.sup.1 -R.sub.f -O-Ar-C(O)PhF
wherein
R.sup.1 is a monovalent radical selected from the group consisting of
fluoride, unsubstituted aryloxys, substituted aryloxys, unsubstituted
arylthios, substituted arylthios, perfluoroalkoxys, and perfluoro (3,
6-dimethyl-1, 4-dioxanyl-2-oxy),
R.sub.f is a hydrogen perfluoroalkyl divalent radical having from 2 to 10
carbon atoms inclusive, and
Ar is an aryl radical, with
(b) a reactant selected from the group consisting of alcohols, metallic
salts of alcohols, and mercaptans.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of this invention are hydrogen-perfluoroalkyl aromatic ethers
having the following structure:
R.sup.1 -R.sub.f -O-Ar-R.sup.2.
R.sup.1 is a monovalent radical selected from the group consisting of
fluoride, unsubstituted aryloxys, substituted aryloxys, unsubstituted
arylthios, substituted arylthios, perfluoroalkoxys, and perfluoro (3,
6-dimethyl-1, 4-dioxanyl-2-oxy),
R.sup.2 is a monovalent radical selected from the group consisting of
hydrogen, halides, cyano, nitro, unsubstituted alkyls having from 1 to 10
carbon atoms inclusive, perfluoroalkyls having from 1 to 10 carbon atoms
inclusive, perfluoroalkoxys having from 1 to 10 carbon atoms inclusive,
substituted and unsubstituted hydrogen perfluoroalkoxy aryloxys,
substituted and unsubstituted hydrogen perfluoroalkoxy arylthios,
unsubstituted alkoxys having from 1 to 8 carbon atoms inclusive,
unsubstituted aryls, substituted aryls, unsubstituted aryloxys,
substituted aryloxys, unsubstituted alkylthios, substituted arylthios,
unsubstituted arylthios, substituted and unsubstituted arylketones,
substituted and unsubstituted arylsulfones, and substituted and
unsubstituted alkylcarboxys.
The R.sub.f radical is a straight-chain or branched hydrogen perfluoroalkyl
divalent and alkyl radical having no unsaturation and from 2 to 10 carbon
atoms inclusive. Preferably, R.sub.f has from 2 to 6 carbon atoms
inclusive and, more preferably, 3 carbon atoms. The R.sub.f radical may be
bonded to the aryloxy structure at any one of its carbon atoms. The
hydrogen of the R.sub.f radical may be bonded to any one of the carbon
atoms of the alkyl radical. Typically, however, the aryloxy is bonded to
the alpha carbon of the R.sub.f radical, and the hydrogen is bonded to the
beta carbon.
Ar is an aryl radical and may be, for example, phenyl, biphenylyl,
naphthyl, pyridyl, pyrimidinyl, triazenyl, and the like.
More specifically, R.sup.1 may be --OPhR.sup.2 z;--OXOR.sub.f OPhR.sup.2 z;
--SPhR.sup.2 z; --ONpR.sup.2 z; --OPyR.sup.2.sub.z ; and--(OCF.sub.2
CFR.sup.3).sub.m F, wherein:
R.sup.3 is a monovalent radical selected from the group consisting of --F
and perfluoroalkyls,
X is a divalent radical selected from the group consisting of -Ph- and
PhQPh,
Q is a divalent radical selected from the group consisting of --CH.sub.2
--, --C(CF.sub.3).sub.2 --, --C(CH.sub.3).sub.2 --, --SO.sub.2 --, --CO--,
--S--, --O--, --PhC(CF.sub.3).sub.2 Ph--; and --PhC(CH.sub.3).sub.2 Ph--;
Ph is the phenyl radical, Np is the naphthyl radical, Py is the pyridyl
radical, m is from 1 to 20 inclusive, preferably from 1 to 10 inclusive,
and z is from 1 to 2 inclusive.
R.sup.2 may be --(OPh).sub.n ; --OPhR.sup.4.sub.z ; --OR.sub.f
OPhR.sup.4.sub.z ; --ORfSPhR.sup.4.sub.z ; --OR.sub.f ONpR.sup.4.sub.z ;
--OR.sub.f OPyR.sup.4.sub.z ; and --C(O)PhR.sup.5.sub.z ; wherein:
R.sup.4 is a monovalent radical selected from the group consisting of
hydrogen, halides, cyano, nitro, unsubstituted alkylthios, substituted
alkylthios, unsubstituted alkyls, perfluoroalkyls, and perfluoroalkoxys,
R.sup.5 is a monovalent radical selected from the group consisting of
fluoride, unsubstituted aryloxys, substituted aryloxys, unsubstituted
arylthios, and substituted arylthios,
Ph is the phenyl radical, Np is the naphthyl radical, Py is the pyridyl
radical, n is from 1 to 4 inclusive, and z is from 1 to 2 inclusive.
"C(O)" e.g. in the radical --C(O) pHR.sup.5.sub.z refers to a ketone.
Specific examples of R.sup.5 include --OPhR.sup.7.sub.z,--SPhR.sup.7.sub.z,
--OPyR.sup.7.sub.z, and --ONpR.sup.7 z, wherein R.sup.7 is a monovalent
radical selected from the group consisting of hydrogen, halides, nitro,
cyano, unsubstituted alkyls, substituted alkyls, unsubstituted alkoxys,
substituted alkoxys, unsubstituted aryls, and substituted aryls, and
unsubstituted aryloxys.
When a radical, such as R.sup.2, occurs twice in the same compound, the two
radicals may be the same or different. For example, R.sup.2 occurs twice
in the compound R.sup.1 -R.sub.f -O-Ar-R.sup.2 where R.sup.1 is
--OPhR.sup.2.sub.z. The two R.sup.2 's in this compound may be the same or
different.
Preferably, the compounds of this invention are stable up to temperature of
at least about 300.degree. C. as measured using a differential scanning
calorimeter (DSC) at 200 psi. Generally, the DSC test indicates the
temperature at which degradation of the compound begins.
The compounds of this invention may be liquid or solid at room temperature.
If the compound is to be used as a lubricant base stock and not as a
lubricant additive, the compound should be a liquid at the temperature of
use.
Preferred compounds of the invention include
(a) benzophenones having the structure:
R.sup.6 PhC(O)PhOR.sub.f R.sup.6 ;
(b) sulfides having the structure:
R.sup.6 PhOR.sub.f OPhSPhOR.sub.f OPhR.sup.6 ;
(c) benzosulfones having the structure:
R.sup.6 PhOR.sub.f OPhSO.sub.2 PhOR.sub.f OPhR.sup.6 ;
(d) benzene-containing compounds having the structure:
R.sup.6 PhOR.sub.f OPhOR.sub.f OPhR.sup.6 ;
(e) bisphenol derivatives having the structure:
PhOR.sub.f OPhAPhOR.sub.f OPh; and
(f) ethers having the structure:
R.sup.6 PhOR.sub.f OPhOPhOR.sub.f OPhR.sup.6,
wherein
R.sup.6 is a monovalent radical selected from the group consisting of
hydrogen, halides, substituted and unsubstituted alkyls, unsubstituted and
substituted alkoxys, substituted and unsubstituted aryloxys, and
substituted and unsubstituted arylthios,
R.sub.f is defined as hereinbefore,
A is a divalent radical selected from the group consisting of
--C(CF.sub.3).sub.2 -- and -- C(CH.sub.3).sub.2 --, and
Ph is the phenyl radical.
More specifically, preferred compounds include
(a) benzophenones selected from the group consisting of
4-fluoro-4'-(1, 1, 2, 3, 3, 3-hexafluoropropoxy)benzophenone;
4-fluoro-4'-(1-(3-methoxyphenoxy)-1,2,3,3,3-pentafluoropropoxyl)benzophenon
e;
4-fluoro-4'-(1-(3-phenoxyphenoxy)-1,2,3,3,-pentafluoropropoxy)benzophenone;
4-phenylthio-4'-(1-(3phenoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)benzophen
one;
4- fluoro-4'- (1-phenylthio-1,2,3,3,3-pentafluoropropoxy)benzophenone;
4-(3-trifluoromethylphenoxy)-4'-(1-(3-phenoxyphenoxy)-1,2,3,3,3-pentafluoro
propoxy)benzophenone; and
4-(3-phenoxyphenoxy)-4'-(1-phenoxy-1,2,3,3,3-pentafluoropropoxy)benzophenon
e;
(b) sulfides selected from the consisting of
bis(4-(3-methoxyphenoxy-1,2,3,3,3-pentafluoropropoxy)phenyl) sulfide; and
bis (4-(1-phenoxy-1,2,3,3,3-pentafluoropropoxy)phenyl)sulfide;
(c) bis (4-(1-phenoxy-1,2,3,3,3-pentafluoropropoxy)phenyl) benzosulfone;
(d) benzene-containing compounds selected from the group consisting of
1,3-bis(1-(3-phenoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)benzene; and
1,3-bis(1-phenoxy-1,2,3 3-pentafluoropropoxy) benzene;
(e) bisphenol derivatives selected from the group consisting of
2,2-bis(4-(1-phenoxy-1,2,3,3,3-pentafluoropropoxy)phenyl) propane; and
2,2-bis(4-(1-phenoxy-1,2,3,3,3-pentafluoropropoxy)phenyl)-1,1,1,3,3,3-hexaf
luoropropane; and
(f) ethers selected from the group consisting of
bis(4-(1-(4-(1,1-dimethylethylphenoxy)-1,2,3,3,3-pentafluoropropoxy)phenyl)
ether; and
bis(4-(1-(3-phenoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)phenyl) ether.
Other preferred compounds of the invention include
1,1,1,3,3,3-hexafluoro-2,2-bis(4-(1,2,3,3,3-pentafluoro-1-phenoxypropoxy)p
henyl)propane, 1,3-bis(4-(1,2,3,3,3-pentafluoro-1-phenoxypropoxy)benzene,
1-(3-phenoxy-phenoxy)-1-(3-(3-phenoxyphenoxy)phenoxy)-1,2,3,3,3-pentafluor
opropane,
4-phenylthio-4'-(1-(3-methoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)benzoph
enone, 4-phenoxy-4'-(1-phenoxy-1 ,2,3,3,3-pentafluoropropoxy)benzophenone,
4-(3-phenoxyphenoxy)-4'-(1,1,2,3,3,3-hexafluoropropoxy)benzophenone, and
4-(2-pyridyloxy)-4'-(1-phenoxy-1,2,3,3,3-pentafluoropropoxy)benzophenone.
A general class of preferred compounds is 4-fluoro-4'-(1-(substituted
aryloxy)-hydrogenperfluoroalkoxy) benzophenones having the structure:
R.sup.1 --R.sub.f --O--Ar--C(O)PhF
wherein R.sup.1 is a monovalent radical selected from the group consisting
of fluoride, unsubstituted aryloxys, substituted aryloxys, unsubstituted
arylthios, substituted arylthios, perfluoroalkoxys, and perfluoro (3,
6-dimethyl-1, 4-dioxanyl-2-oxy), R.sub.f is a hydrogen perfluoroalkyl
divalent radical having from 2 to 10 carbon atoms inclusive, and Ar is an
aryl radical. Specific examples of such benzophenones include 4-fluoro-4'-
(1-(3-methoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)benzophenone;
4-fluoro-4'-(1,1,2,3,3,3-hexafluoropropoxy) benzophenone;
4-fluoro-4'-(1,2,3,3,3-pentafluoro-1-phenylthiopropoxy)benzophenone,
4-fluoro-4'-(1,2,3,3,3-pentafluoro-1-phenylpropoxy) benzophenone,
4-fluoro-4'-( 1-(3-phenoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)
benzophenone,
4-fluoro-4'-(1-(6-chloropyridinyloxy)-1,2,3,3,3-pentafluoropropoxy)benzoph
enone, and 4-fluoro-4'-(1-(2-naphthyloxy)-1,2,3,3,3-pentafluoropropoxy)
benzophenone. These compounds have utility not only as lubricants
themselves but also as intermediates for the production of new
extended-temperature-range lubricating compounds.
Generally, the compounds of this invention are made by the base-catalyzed
addition of hydroxy-substituted aryl compounds, such as phenols, to
terminal perfluoroolefins, such as aryloxyperfluoroalkenes or
arylthioperfluoroalkenes.
The terminal perfluoro olefins may be prepared by any one of a number of
known methods disclosed in, e.g., Nippon Kaoaku Kai-shi, Vol. 1975, No. 2,
pp. 311-315; U.S. Pat. No. 3,180,895; and Japanese patent disclosures
50-117727 and 62-153236, which documents are hereby incorporated by
reference.
A preferred method of making a terminal perfluoro olefin, such as an
aryloxy perfluoroalkene, includes (a) reacting a phenol with sodium in a
solvent such as glyme to form a phenoate, (b) reacting the phenoate with a
perfluoroalkene at subzero temperatures, e.g., -40.degree. C., and (c)
purifying the resulting product by distillation. Alternatively, a
dihydroxybenzene or a bisphenol may be used in place of the phenol. In
these later cases, two moles of perfluoroalkene react to each mole of
dihydroxybenzene or bisphenol.
Preferably, the reaction between the hydroxy-substituted aryl compound and
the terminal perfluoro olefin is performed in a dipolar aprotic solvent,
such as acetonitrile, dimethylsulfoxide, dimethylformamide,
N-methylpyrrolidone, or diphenyl sulfone. Dimethylformamide and
acetonitrile are the most preferred solvents. In some reactions, such as
those which use a highly perfluorinated olefin, it is desirably to use a
cosolvent, such as a chlorofluorohydrocarbon, e.g. "FREON" 113. "FREON"
products are available from E. I. du Pont de Nemours & Co., Inc.,
Wilmington, Del., owner of the trademark "FREON".
Many types of bases may be employed in the reaction. Examples of suitable
bases include alkali carbonates, alkali hydrogen carbonates, alkaline
earth carbonates, alkali hydroxides, alkaline earth metal hydroxides, and
amine bases, such as triethylamine. The most preferred bases are weak
bases, such as potassium carbonate and triethylamine.
A catalytic amount of the base, e.g., about 0.05 to about 0.2 molar
equivalent per 100 moles of the terminal perfluoroolefin, is sufficient
for the reaction to proceed. However, a molar equivalent or more of the
base is preferred for a significantly shorter reaction time.
The reaction is desirably performed at ambient conditions, but may be
performed at temperatures from about 0.degree. to about 200.degree. C. at
atmospheric, sub-atmospheric or superatmospheric pressures.
The reaction time depends on the variables of the reaction, such as the
nature of the solvent, the amount of base employed, and the temperature.
Typically, the reaction time ranges from about to about 24 hours at
ambient temperature.
As mentioned hereinabove, a class of compounds of the invention, namely,
the 4-fluoro-4'-(1-(substituted aryloxy)-hydrogenperfluoroalkoxy)
benzophenones, may be used as intermediates for the production of new
extended-temperature-range lubricating compounds. These benzophenones may
be reacted with alcohols, metallic salts of alcohols, or mercaptans under
basic conditions, preferably in a dipolar aprotic solvent. Suitable bases
and amounts for catalyzing the reaction and suitable dipolar aprotic
solvents are the same as those listed hereinabove. The reaction may be
performed at temperatures ranging from about 0.degree.-200.degree. C., but
preferably at about 20.degree.-100.degree. C. After the reaction is
complete, the solid byproducts are filtered out, and low boiling materials
are removed by distillation. The product may be purified further by
distillation techniques.
The compounds of this invention are useful as lubricants over extended
temperature ranges. They may be used alone and also may be used in
conjunction with various additives to improve their performance.
Additionally, they may themselves be used as additives with other base
stocks.
When used as an additive to a base stock, the compounds of the present
invention must be compatible with the base stock. By compatible, it is
meant that the compounds of the present invention may be readily dispersed
or dissolved in the base stock, either with or without the addition of an
appropriate surfactant. Examples of known base stocks useful in
conjunction with the compounds of this invention include organic oils and
greases well known to those skilled in the art. When the compounds of the
present invention are used as additives to conventional, compatible base
stocks, it is preferred that the base stocks are polyglycols, polyphenyl
ethers and polyol esters. It is more preferred that the base stocks are
polyphenyl ethers, such as 5P4E which is a polyphenyl ether having five
phenyl groups and four ether linkages. Other preferred base stocks include
polyol esters such as pentaerythritol tetra C.sub.5-9 esters (PET).
Lubricant compositions of this invention comprise from about 0.1 to about
100 weight percent of the compounds of the invention. That is, the
compounds of this invention may be used as a lubricant base stock or they
may be used as additives with other base stocks.
When the compounds of this invention are used as lubricant additives, it is
preferred that they are used in amounts of at least about 0.5 weight
percent, more preferably at least about 50 weight percent. It is also
preferred that the compounds of the present invention, when used as
additives, are used in amounts of no greater than about 50 weight percent,
preferably no greater than about 20 weight percent.
As discussed above, the compounds of the present invention may be used as
lubricant base stocks themselves, either alone or with the addition of
additives known in the art. The preferred additives are functional
additives which can increase stability and/or provide resistance to
corrosion. When used as the lubricant base stock with additives, it is
preferred that the compound of this invention comprise at least about 50
weight percent, more preferably at least about 95 weight percent of the
composition with one or more additives making up the remainder of the
lubricant composition. Additionally, the compounds of this invention may
be blended with other base stocks to prepare lubricants.
Thus, there is provided in accordance with the present invention, new
lubricating compounds which are stable at high temperatures, which are
highly soluble in organic oils and/or greases, and which may be prepared
by relatively simple methods in high yields. Also provided by this
invention are lubricant compositions containing such lubricating compounds
and a method for preparing such lubricating compounds.
The following examples are illustrative only and should not be construed as
limiting the invention which is properly delineated in the appended
claims.
EXAMPLES
Example 1
Preparation of 1,3-bis(1-phenoxy-1,2,3,3,3-pentafluoropropoxy)benzene
11 g 1,3-dihydroxybenzene, 15 g potassium carbonate, 100 ml
dimethylformamide, and 20 g 1-(1,2,3,3,3-pentafluoro-1-propenyloxy)benzene
were added to a flask and reacted by stirring at room temperature for six
hours. 200 ml methylene chloride and 500 mls water were admixed with the
reacted mixture. The reacted mixture was phase-separated from the aqueous
phase and washed and separated two more times with 100 ml water per wash.
The washed reacted mixture was then dried over sodium sulfate, filtered,
and distilled to remove low-boiling compounds. The distilled product was
further distilled to produce the desired benzene having a boiling point of
175.degree. C. at 0.6 mm Hg.
Example 2
Preparation of 1,1,1,3,3,3-hexafluoro-2,2-bis
(4-(1,2,3,3,3-pentafluoro-1-phenoxypropoxy)phenyl)propane
17 g 4,4'-(hexafluoroisopropylidene) diphenol, 100 ml dimethylformamide, 14
g potassium carbonate, and 30 g 1-phenoxy perfluoropropene were added to a
flask and reacted by stirring for four hours at room temperature. The
mixture was then stirred for an additional hour at 50.degree. C., then
cooled to room temperature. After cooling, 100 ml methylene chloride and
250 ml water were admixed with the reacted mixture. The reacted mixture
was separated from the aqueous phase by phase separation techniques. The
reacted mixture was washed again with 150 ml water and separated from the
aqueous phase, dried over sodium sulfate, and filtered. The product was
purified from the reacted mixture by distilling to 240.degree.-280.degree.
C. to remove the low-boiling compounds. NMR spectra indicated the product
to be about 90% of the desired propane. The process resulted in a 25%
yield. Differential scanning calorimetry of the product indicated that the
propane product is stable up to 340.degree. C. under 200 psi oxygen
pressure, suggesting a high degree of thermo-oxidative stability.
Example 3
Preparation of
1-(3-phenoxyphenoxy)-1-(3-(3-phenoxyphenoxy)phenoxy-1,2,3,3,3-pentafluorop
ropane
7 g 3-phenoxy-3-phenoxyphenol, 10 g 1-(3-phenoxyphenoxy)perfluoropropene,
100 ml dimethylformamide, and 4 g potassium carbonate were added to a
flask and reacted by stirring for three hours at room temperature. The
reacted mixture was then allowed to stand overnight. 250 ml water and 200
ml methylene chloride were admixed into the reacted mixture. The reacted
mixture layer was separated from the aqueous layer and again washed with
200 ml water. The reacted mixture layer was again separated from the
aqueous layer, dried over sodium sulfate, filtered, and distilled to
produce an oil having a boiling point of about 280.degree. C. at 0.5 mm
Hg. The process resulted in a 47% yield of the desired propane.
Differential scanning calorimetry of the product indicated that the ethane
product is stable up to 343.degree. C. under 200 psi oxygen pressure,
suggesting a high degree of thermo-oxidative stability.
Example 4
Preparation of
1-(m-(m-phenoxyphenoxy-m-phenoxyphenoxy)phenoxy)-2-H-2-(3,6,9-trimethyl-1,
4,7-trioxa-1-perfluorononyl)-1,1,2-trifluoroethane
3.2 g 1-(m-(m-phenoxyphenoxy-m-phenoxyphenoxy))phenol, 5.0 g
2-(3,6,9-trimethyl-1,4,7-trioxa-1-perfluorononyl)-1,1,2-trifluoroethylene,
2.0 g potassium carbonate and 15 ml dimethylformamide were reacted by
stirring the ingredients together for 12 hours at ambient temperature. 50
ml water and 50 ml ethyl acetate were admixed into the reacted mixture for
a few minutes. The reacted mixture layer was then separated from the
aqueous layer, dried over magnesium sulfate, and solvent-evaporated. Flash
chromotography indicated that the product was the desired ethane prepared
at 95.5% yield. Differential scanning calorimetry of the product indicated
that the ethane product is stable up to 470.degree. C. under 200 psi of
oxygen pressure, suggesting a high degree of thermo-oxidative stability.
Example 5
Preparation of
1-(m-methoxyphenoxy)-2-H-2-(3,6,9-trimethyl-1,4,7-trioxa-1-perfluorononyl)
-1,1,2-trifluoroethane
11.6 g m-methoxyphenol, 56.5 g
2-(3,6,9-trimethyl-1,4,7-trioxa-1-perfluorononyl)-1,1,2-trifluoroethylene,
18 g potassium carbonate, and 100 ml acetonitrile were stirred together
for 16 hours at ambient temperature to allow the ingredients to react.
Water washing and extraction with ethyl ether as described in Example 4
was completed. Yield of the desired ethane was 98%.
Example 6
Preparation of
1-(m-hydroxyphenoxy)-2-H-2-(3,6,9-trimethyl-1,4,7-trioxa-1-perfluorononyl)
-1,1,2-trifluoroethane
50 g boron tribromide are added dropwise to a mixture of 67.0 g of the
ethane product form Example 5 and 200 ml methylene chloride held at a
temperature of -10.degree. C. in a nitrogen atmosphere. The mixture was
stirred at ambient temperature for 2 hours to allow the ingredients to
react. The mixture was then quenched by adding ice and acidified with 200
ml 2N HCl. The product was extracted with ether and distilled at
110.degree.-120.degree. C. and 0.5 mm Hg. Yield of the desired ethane was
87.6%.
Example 7
Preparation of
1-(m-(m-phenoxyphenoxy-m-phenoxyphenoxy)phenoxy)-2-H-2-(perfluoro-3,6
-dimethyl-1,4-dioxanyl-2-oxy)-1,1,2-trifluoroethane
1-(m-(m-phenoxyphenoxy-m-phenoxyphenoxy))phenol and
perfluoro-2-ethenyloxy-(3,6-dimethyl)-1,4-dioxane were reacted according
to the procedure in Example 4, resulting in a 92% yield of the desired
ethane. The dioxane was prepared by the pyrolysis of perfluoro
-(3,6-dimethyl-1,4-dioxanyl-2-oxy) propionic acid potassium salt which, in
turn, was prepared by the hydrolysis of the corresponding acid fluoride
made according to U.S. Pat. No. 4,033,984. The boiling point of the ethane
product was determined to be 230.degree.-240.degree. C. at 1 mm Hg.
Example 8
Preparation of 4-fluoro-4' (1,1,2,3,3,3-hexafluoropropoxy)benzophenone
43 g 4-fluoro-4'-hydroxybenzophenone, 30 g potassium carbonate, and 400 ml
acetonitrile were mixed in a flask and cooled to about 0.degree. C. 45 g
perfluoropropene were bubbled into the cooled mixture over about a
45-minute period. After the addition of the perfluoropropene, the mixture
was stirred for four hours while it warmed to room temperature. Solids in
the mixture were removed by filtration, and acetonitrile was removed by
distillation. The product was distilled again at 160.degree.-165.degree.
C./0.5 mm Hg pressure. Gas chromatography confirmed that the product was
the desired benzophenone.
Example 9
Preparation of
4-fluoro-4'(1-(3-methoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)benzophenone
35 g 3-methoxyphenoxyperfluoropropene, 19 g potassium carbonate, 22 g
4-hydroxy-4'-fluorobenzophenone, and 150 ml dimethylformamide were reacted
by stirring together for 6 hours at room temperature, followed by eight
hours at 70.degree.-75.degree. C. Solids in the reacted mixture were
removed by filtration, and low-boiling compounds were removed by
distillation at 150.degree. C./0.5 mmHg. The resulting product was shown
by gas chromatography to be the desired benzophenone, having a boiling
point of about 220.degree. C. at 0.5 mm Hg.
Example 10
Preparation of
4-fluoro-4'-(1-(3-phenoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)benzophenon
e
22 g 4-hydroxy-4'-fluoro-benzophenone, 19 g potassium carbonate, 40 g
3-phenoxyphenoxy perfluoropropene, and 150 ml dimethylformamide were
reacted by stirring the ingredients together for eight hours at
80.degree.-90.degree. C. After cooling the reaction mixture to room
temperature, the solids in the reaction mixture were removed by
filtration, and the solvent was distilled off under reduced pressure at
100.degree. C. The product was further distilled at
212.degree.-250.degree. C. and 0.5 mm Hg. The process resulted in a 61%
yield of the desired benzophenone product, confirmed by gas
chromatography.
Example 11
Preparation of
4-phenylthio-4'-(1-(3-methoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)benzoph
enone
33 g
4-fluoro-4'-(1-(3-methoxyphenoxy)-1,2,3,3,3-pentafluoro-propoxy)benzopheno
ne, 10 g potassium carbonate, 7.7 g thiophenol, and 100 ml
dimethylformamide were stirred together for eight hours at 100.degree. C.,
then allowed to cool to room temperature. After cooling, the solids were
removed from the mixture by filtration, and the low boilers were removed
by distillation at 200.degree. C./0.5 mm Hg. The resulting product was
distilled at 240.degree.-300.degree. C./0.5 mm Hg. NMR spectra and gas
chromatography confirmed that the desired benzophenone was prepared.
EXAMPLE 12
Evaluation of lubricating properties of various hydrogenperfluoroalkyl
aromatic ethers of this invention
The anti-wear and extreme pressure characteristics of compositions
containing some of the compounds of this invention were measured using a
four-ball test using a Falex friction and wear tester, available from
Faville-Levally Corp. Downers Grove, Ill. The compositions tested included
mixtures of polyphenylether 5P4E and a selected level of the compound of
the invention. Table 1 provides the particular compound of the invention
employed and the weight percent added to the polyphenylether 5P4E.
In Table 1, Compound #1 refers to
bis(4-(3-methoxyphenoxy-1,2,3,3,3-pentafluoropropoxy)phenyl)sulfide,
Compound #2 refers to
1,3-bis(1-(3-phenoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)benzene,
Compound #3 refers to
bis(1-(4-t-butylphenoxy)-1,2,3,3,3-pentafluoropropoxy phenyl)ether,
Compound #4refers to
(4-(1-phenoxy)-1,2,3,3,3-pentafluoro-propoxy)phenyl)sulfide, Compound #5
refers to 4, 4'-bis(1-phenyl-1,2,3,3,3-pentafluoropropoxy)benzosulfone,
and Compound #6 refers to
4-phenylthio-4'(1'-(3-methoxyphenoxy)-1,2,3,3,3-pentafluoropropoxy)
phenylbenzophenone.
The four ball-bearing balls used in the test were made of M50 steel. The
test load was 15 kg (33.1 lbs), and the temperature was held at
300.degree. C. The test speed was 1200 rpm, and each test was run for one
hour. About 60 cubic centimeters of fluid were used for each test. During
each test, the torque as a function of the wear cycles was monitored on a
real time data acquisition basis for data analysis to yield the
coefficient of friction. Optical microscope pictures of the bearing balls
were taken at the test completion and scar diameter was measured from
these pictures. Table 1 provides the wear scar value and coefficient of
friction of each test run.
TABLE 1
______________________________________
Coefficient
Wt % Wear Scar of
Compound # In Oil Value (mm) Friction
______________________________________
None 0.0 2.61 0.197
1 0.3 0.43 0.065
1 5.0 0.34 0.041
1 9.5 0.29 0.036
1 35.0 0.28 0.057
2 1.0 2.02 0.158
3 1.0 1.62 1.163
4 1.0 0.55 0.068
5 1.0 1.67 0.120
6 1.0 1.62 0.180
______________________________________
While our invention has been described in terms of a few specific
embodiments, it will be appreciated that other embodiments could readily
be adapted by one skilled in the art. Accordingly, the scope of our
invention is to be considered limited only by the following claims.
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